Dipyridinium derivatives of esterified oxyalkylated diphenylol methanes



Patented Aug. l, 1950 UN I TE DIPYRIDINIUM DERIVATIVES OF ESTERI- FIED' OXYALKYLATED DIPHENYLOL METHANES Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, poration of Delaware No Drawing. Original a Serial No. 586,263. Di

tion November 26,

DeL, a corpplication April 2, 1945, vided and this applica- 1945, Serial No. 630,978

Claims. (Cl. 260-295) This invention relates to a new chemical product or compound and to the manufacture of same, our present application being a division of our pending application Serial No. 586,263, filed April 2, 1945, now Patent No. 2,429,997.

One object of our invention is to provide a new material or composition of matter, that is particularly adapted for use as a demulsifler in the resolution of crude oil emulsions, but which is also capable of use for various other purposes, or in various other arts.

Another object of our invention is to provide a practicable method for manufacturing or producing the new material or composition of matter above referred to.

The new material or composition of matter herein described consists of a hydrophile dipyridinium compound of the formula:

Halogen Halogen in which R5 is a radical selected from the class consisting of methylene and hydrocarbon substituted methylene radicals having not over 7 carbon atoms; R is the radical obtained by the removal of an alpha-hydrogen atom from the acid radical of a, low molecular weight monocarboxy acid ester of a phenoxyalkanol of the formula:

R (R) nH in which R1 is a substituted monocyclic phenyl radical having 2 of the 3 reactive 2,4,6 positions substituted by two alkyl side chains, of which at least one contains at least 3 carbon atoms, and the longest of which does not contain more than 8 carbon atoms; R20 is an alkoxy radical selected from the class consisting of --C2H4O-- and -C3HsO-- radica1s;,and n is a small whole number varying from 1 to 3, or even 4 or 5, or more, for instance, 6. More specifically, the ester, derived from a compound in which a methylene bridge, or the like, unites the residues of two phenoxyalkanols, includes alkanol radicals, in which the carbon atom chain is interrupted at least once by oxygen, i. e., etheralkanols or etheralcohols. More specifically, then, R in the first formula of the text represents the divalent radical by elimination of a nuclear hydrogen atom and a halogen from the ester of the formula:

in which all of the symbols have their prior signiflcance, and OCRs Halogen is the acyl radical of a low molecular weight alphachloromonocar- 5B boxy acid, such as chloroacetic acid. In other words, repeating the previous example with specific reference to chloroacetic acid, the formula becomes:

R10 (R20) nOC-CHEC].

The preparation of our new material of composition of matter, contemplates four steps: The first step consists in reacting two moles of a properly selected substituted phenol with one mole of an aldehyde, so as to produce a diphenylolmethane or substituted methane. The preferred aldehyde is formaldehyde, on account of its reactivity and low cost. Other aldehydes which may be used are acetaldehyde, propionaldehyde, butyraldehyde, and furiural. The condensation reactions of this type are well known and do not require description. In the case of iurfural, it is desirable to use alkaline condensing agents, but in the other instances, acid or acidic substances are usually employed. Since these condensation reactions cannot produce resins in the usual sense, they are comparatively simple and result in oils varying from moderately viscous substances to oils so viscous as to appear to be almost solid.

The phenols are selected so that resinification does not take place, insofar that the phenols are limited to types in which there is only one reactive nuclear hydrogen atom. Specifically, then, the phenols may be indicated by the following formula:

H H 0 O in which R5 is a radical selected from the class consisting of methylene and hydrocarbon substituted methylene radicals having not over 7 carbon atoms and is preferably the unsubstituted methylene radical derived from formaldehyde.

As to the most suitable phenols, we prefer to use 2-4-diamyl phenol or p-tert-butyl-o-cresol. Other suitable phenols include (l-methyl-butyl)-ortho-cresol (l-ethyl-propyl)-ortho-cresol (See U. S. Patent No. 2,073,995, dated March 16, 1937, to Raiziss et a1. See also U. S. Patent No. 2,106,750, dated February 1, 1938, to Raiziss et a1.)

Other phenols can be prepared by the aikylation of orthoor paracresol by the same procedure as is employed forthe alkylation of phenol. (See U. S. Patent No. 2,060,573, dated November 10, 1936, to Hester.)

We have found that 2,4-dipropylphenol is also an excellent raw material. (See also U. S. Patents Nos. 2,064,885, dated December 22, 1936, to Carpenter; 2,104,412, dated January 4, 1938, to Buc; and 2,207,753, to Moyle et al., dated July 16,1940.)

It is understood that there is no objection to the presence of an additional alkyl radical, provided its presence still leaves a reactive nuclear hydrogen atom. Such alkyl radical, if present, is limited to radicals having not over 8 carbon atoms, and must occupy one of the 3 or 5 positions. For all practical purposes, however, such compounds are derived from meta-cresol or similar homologs, and thus, for the sake of brevity in the hereto appended claims, such alkyl groups will be indicated as being in either the 3 position, or in the 5 position. However, it is understood that the 3 and 5 positions are the obvious equivalents. One such example would be the product obtained by the propylation of metacresol. The meta group does not occupy a reactive position, and its presence does not interfere with subsequent reaction. In a few instances, compounds are obtainable where a cyclic radical may serve instead of an alkyl radical, for example, in 4-tert-butyl- 2-phenylphenol or 4-tert butyl 2 cyclohexylphenol.

Since the substituted phenols employed as re- 4 PHENOL ALDEHYDE CONDENSATION Example 1 Pounds Diamyl(2,4) phenol 702 Formalin 40% U. S. P. 114 Concentrated hydrochloric acid 3.3 Alkylated aryl sulphonic acid salt (Nacconal N. R. S. F.) 33

The mixture is stirred vigorously under a reflux condenser at approximately 105 C. for approximately 2 hours. The temperature is then raised to approximately 150-160 C. and held at this temperature for about the same period of time.

PI-IENOL ALDEHYDE CONDENSATION Example 2 The same procedure is employed as in the previous example, except that 618'pounds of dipropyl(2,4) phenol replaces the 702 pounds of diamylphenol used in the preceding example.

PHENOL ALDEHYDE CONDENSATION Example 3 The same procedure is followed as in the two previous examples, except that one uses a mixture consisting of 351 pounds of diamyl(2,4)phenoi and 309 pounds of dipropyl(2,4)phenol. The result of such mixture is, that the condensate is actants are invariably water-insoluble, and since formaldehyde, a water-soluble aldehyde, is the preferred reactant for introducing the methylane bridge, or its equivalent, we have found it most desirable to employ the procedure described in U. S. Patent No. 2,330,217, dated September 28, 1943, to Hunn. Briefly stated, this procedure includes the use of an acid cata yst along with an emulsifying agent to promote emulsification, and thus, reaction between the water-insoluble phenol and the water-soluble aldehyde. As an example of such procedure, the following is included:

also a mixture, of which one-third corresponds to Example 1, preceding, one-third to Example 2, preceding, and the remaining one-third represents the type of compound, in which the phenol nuclei are different, one being an amylated nucleus and the other a propylated nucleus.

Due to ready availability, and other desirable properties, it is particularly convenient and economical to replace dipropyl(2,4)phenol with an equivalent amount of 4,6-di-tertiary-butyl-mcresol, which is indicated by the following formula:

CH.|\ OH 01170 CH3 ogtaom In the second step, a properly selected phenol of the kind typified by the formula:

alkyl- R 1 alkyln1 If one employs 2 moles of ethylene oxide, the reaction may be indicated in the following manner:

chlorine chlorine N rndcoommo 00.11.00 (Lora-N alkyl-- R kyl alkyl- 1 As suggested, one may not only use pyridine, but other homologs of pyridine, that is, members of the pyridine series. For instance, members of the pyridine series suitable as reactants include pyridine and methylated pyridines, i. e., pyridine in which'l, 2 or 3 methyl groups have been substituted in the nucleus, such as picolines, lutidines and collidines. Coal tar bases represent mixtures of suitable heterocyclic materials which may be used as such, or after suitable pyrification, without separation into the individual compounds.

While chloroacetic acid or chloroacetyl chloride is the preferred halogen carboxylic acid compound, other halogen acids, halogen substituted acyl halides, and esterifying derivatives are suitable, particularly a-halogen carboxylic acids of not over six carbon atoms. When the halogen is in the a-position to the CO group, the reaction seems to go with greater readiness. With the shorter chain esterifying halogen carboxylic acids or their functional equivalents, especially chloroacetyl chloride, the reaction goes with great ease. Other halogen acylating compounds which are suitable are, for example: a-chloropropionic acid, etc., but especially any acid of the formula:

methyl, ethyl or procedure. Such compound are frequently oxy--v ethylated so as to render them water-soluble. In the present instance, instead of treating one mole of the selected phenol with a large ratio of oxye alkylating agent, one employs instead a comparatively low ratio, as indicated by the value for the letter n in prior formulae. In other words, one treats the phenol with 1 mole, 2 moles, or 3 moles of the oxyalkylating agent. The product so obtained is still distinctly water-insoluble to the extent that it will not yield a sol or solution, and this is also true of the ester derived therefrom. The ester is invariably even less water-insoluble. It is to be noted, however, that such water insoluble or partially soluble product represents the initial oxyalkylation step in the same type of procedure employed to produce a water-soluble product. Thus as an example of various patents which teach the oxyalkylation of water-insoluble phenols including the stepwise addition of the oxyalkylating agent, attention is directed to the following: British Patent No. 470,181, British Patent No. 452,866, U. S. Patent No. 2,243,330, dated May 27, 1941, to DeGroote 8a Keiser, and U. S. Patent No. 2,233,381, dated February 25, 1941, to DeGroote & Keiser.

Having obtained the water-insoluble bis(phenoxyalkanollmethane, or one that is somewhat hydrophile, such product is esterified with. chloroacetyl chloride, chloroacetic acid, bromoacetic acid, alphachloropropionic acid, alpha-chlorobutyric acid, or the like. Such reaction, particularly between the acid itself, as differentiated from the acyl chloride, is simply an esterification reaction with the elimination of water, and is preferably carried out in the presence of an inert solvent insoluble in water, which serves to remove the water of formation. Such procedure is illus trated by numerous patents, including the following: British Patent No. 500,765, U. S. Patent No. 1,732,392, dated October 22, 1929, to Wietzel, and U. S. Patent No. 2,264,759, dated December 2, 1941, to Jones.

Having obtained the diol ester, it is only necessary to react such compound with pyridine, or a pyridine homolog. This reaction takes place readily by refluxing in the presence of an excess of pyridine, and subsequently removing the excess of pyridine which does not enter the reaction, by distillation, and preferably, vacuum distillation. The herein described procedures are illustrated by the following examples:

DI HYDROXYALKYLOXYPHENYL) METHANE Example 1 One pound mole of the product described under the heading Phenol Aldehyde Condensation, Example 1 is treated with 2 pound moles of ethylene oxide, in the presence of one-half of 1% of sodium methylate;.as the reaction proceeds, the sodium methylate either dissolves, or is converted into a soluble compound by chemical combination. Reaction is conducted at approximately 125 C. and -200 pound gauge pressure for approximately 2 to 4 hours, until the reaction appears to be complete, as indicated by the pressure dropping to zero. may beindicated by the following formula:

oc mon pension amylamylceding example, except that 4 pound moles of ethylene oxide are employed instead of 2 pound moles, and the period of reaction is approximately fifty percent longer. 1

DI(HYDROXYALKYLOXYPHENYL) METHANE Ecample 3 The same procedure is employed as in Example 1, immediately preceding, except that 6 pound moles of ethylene oxide are employed instead of 2 pound moles, and the time of reaction is approximately twice that indicated in Example 1. Further oxyethylation, for instance, the use of another 6 pound moles, may be required to give a distinct hydrophile eilect in the final compound.

DI(HYDROXYALKYLOXYPHENYL) METHANE Example 4 The same procedure is employed as in the 3 preceding examples, except that the propylated compound described under the heading "Phenol Aldehyde Condensation, Example 2 is substituted for the amylated derivative employed in the three preceding examples.

DI(HYDROXYALKYLOXYPHENYL) METHANE Example 5 The same procedure is employed as in Examples 1 to 4, preceding, except that propylene oxide is substituted for ethylene oxide.

Previous reference has been made to the fact that the esterification step is carried out in the conventional manner, preferably in the presence of an inert solvent. This simply means that the reactants, to wit, the acid, such as chloroacetic acid, and the bis(phenoxyalkanol)methane, are mixed in equimolar proportions, in the presence of a solvent, in which both are soluble, such as xylene, cymene, decalin, or the like. The mixture is refluxed at some suitable temperature, above 100 C. and below 200 0., so that water of formation resulting from the esterification reaction is carried over as a constant boiling mixture. Such mixed vapor is condensed in the customary manner so that the water is trapped off, measured, and then discarded and the solvent returned to the reaction vessel for further use. Ordinarily, such reactions are catalyzed by the addition of an acidic catalyst, such as toluene sulfonic acid, a cresyl phosphoric acid, dry hydrochloric acid, trichloroacetic acid, or the like. Insofar that the alphachlorocarboxy acids show marked acidity, in comparison with the unchlorlnated carboxy acids, the reaction may be conducted without an added catalyst, if desired, or in the presence of an added catalyst, such as one-half to 1% of toluene sulfonic acid. Such catalyst tends to discolor the final product, but this is often immaterial,

The product so obtained 8 as, for example, when the product is used as a demulsiiier. The entire procedure is too well known to require further elaboration, but is illustrated by the following examples:

ns'rm Example 1 One pound mole of the compound described under the heading Di(Hydroxyalkyloxyphenyl) methane, Example 1," preceding, is mixed with 2 pound moles of chloroacetic acid and the mixture refluxed in the presence of xylene equivalent to about 50%, by volume, of the reaction mass, with an appropriate trap for removal of 2 pound moles of water, at, a temperature of approximately 155 to 225 C. The time required is usually 3 to 10 hours. The resultant is a darkcolored, viscous liquid.

preceding examples, except that a-chloropropionic acid is substituted for a-chloroacetic acid.

' ESTER.

Example 4 Chloroacetylchloride is substituted for the chloroacetic acid employed in Ester, Example The reaction starts to take place rapidly between 45 C. and C. and the temperature should be controlled so the reaction takes place at the lowest suitable temperature. The acylchloride should be added slowly to the di(hydroxyalkzloxyphenonmethane, with constant and vigorous stirring. Hydrochloric acid is formed and should be vented and disposed of in a suitable manner. If the reaction does not take place promptly, the temperature should be raised moderately, for instance, 5 to 15 0., or a bit higher, until the reaction proceeds smoothly. However,

assoon as the reaction does start, the temperature should be lowered until the reaction proceeds at the slowest feasible rate. Generally, this means the use of proper cooling devices, or controlled slow addition of the acyl chloride. Completeness of the reaction can be determined in any suitable manner, such as a check on the amount of hydrochloric acid eliminated, or the drop in hydroxyl value of the reactant mixture. When the reaction is completed, any hydrochloric acid gas dissolved in the reaction mass. should be eliminated by passing an inert gas, such as carbon dioxide, through the mixture.

Having obtained an ester of the kind exempliiied by the previous examples, or the bromo derivative instead of the chloro derivative, the next step simply involves reaction with pyridine or a pyridine homolog of the kind previously described. The reaction takes place fairly rapidly, and usually is complete within 4 to 20 hours, particularly if an excess of pyridine is employed. The esters previously described are invariably viscous or semi-solid masses, which are soluble in pyridine without dii'iiculty.

. 9 DEYRIDMUM HALIDE I Example 1 Due poundmole of the ester described inEs ter, Example 1, preceding. is refluxed with constant stirring with several pound moles, for example, 4 to 6, of technically pure pyridine. The reaction is conducted from approximately 4 to 20 hours, at a temperature in excess of 115 C., or thereabouts, until reaction is complete. Completeness of the reaction can be determined by distilling the uncombined pyridine from a sample, and noting, by difference, percentage of pyridine, which has been combined. Another suitable test is the determination of ionizable halogen, for instance, chlorine. It is to be noted that the reaction converts a non-ionizable halogen atom to an ionizable atom. When the reaction is complete, the excess of pyridine is removed by continuing the stirring and employing vacuum, so as to give a substantially solid or highly viscous, dark-colored mass. This reaction product should show distinct hydrophile properties.

Such compound conforms to the following formula:

chlorine I N moooonioio oonimooom-u DIPYRIDINIUM HALIDE Example 2 The same procedure is followed as in Example 1, preceding, except an ester exemplified by Ester, Example 2 and Ester, Example 3, preceding. is substituted for the ester employed in the previous example.

DIPYRIDINIUM HALIDE Example 3 chlorine The same procedureis followed as in the first alkyl halogen alkylkyl alkyl in which R20 is an alkoxy radical selected from the class consisting of -C2H4O- and -C3HsO-- radicals; n is a small whole number varying from 1 to 6; C.R3 is the acyl radical of a low molecular weight monocarboxy acid having not more than 6 carbon atoms, in which an alpha-hydrogen atom has been removed, linked to the nitrogen of the radical NERi through its alphacarbon atom; NER4 represents a radical of a heterooyclic compound of the pyridine series, selected from the group consisting of pyridine and C-linked methyl homologs of pyridine; R5 is a radical selected from the class consisting of methylene and hydrocarbon substituted methylene radicals having not over 7 carbon atoms; Re is a member of the class consisting of hydrogen atoms and alkyl radicals having not over 8 carphenolic residues are subphenol radicals having 2 of the 3 reactive 2,4,6 positions substituted by 2 alkyl side chains, of which at least 1 contains at least 3 carbon atoms and the longest of which does not contain more than 8 carbon atoms.

The new materials or compositions of matter herein described are useful as wetting, detergent and leveling agents in the laundry, textile, and dyeing industries; as wetting agents and detergents in the acid washing of fruit, in, the acid washing of building stone and brick; as a wetting agent and spreader in the application of asphalt, in road building and the like; as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes, and the like; as germicides', insecticides, emulsifiers for cosmetics, spray oils, water-repellent textile finish, etc. These uses are by no means exhaustive, as far as industrial application goes, although the most important use of our new material is as a demulsifler for water-in-oil emulsions, and more specifically, emulsions of water or brine in crude petroleum. We have found that the chemical compounds herein described, which are particularly desirable for use as demulsifiers, may also be used as a break inducer in doctor treatment of the kind intended to sweeten gasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton.)

Chemical compounds of the kind herein described are also of value as surface tension debon atoms; and the stituted monocyclic pressants in the acidization of calcareous oilbearing strata, by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are effective as surface tension depressants, or wetting agents in the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein described as flooding agents for recovering oil from subterranean strata, reference is made to the procedure described in detail in U. S. Patent No. 2,226,119, dated December 24, 1940, to DeGroote & Keiser. As to using compounds of the kind herein described as dernulsifiers, or in particular as surface tension depressants, in combination with mineral acid or acidization of oil-bearing strata, reference is made to U. S. Patent No. 2,233,383, dated February 25, 1941, to DeGroote 8t Keiser.

The new compounds herein described are of utility, not only for the purposes specifically enumerated in detail, but they also find application in various other industries, processes, and for various uses, where wetting agents of the conventional type are used. As to some of such additional uses which are well known, see The Expanding Application of Wetting Agents, Chemical Industries, volume 48, page 324 (1941).

. Another use for the compounds herein contemplated is in the prevention of landslides, as describedin U, S. Patent No. 2,348,458, dated May 9, 1944, to Endersby.

Reference i made to the fact that the materials, compounds or products herein contemplated are hydrophile in nature, and may vary from self-emulsifiable products, through the range that gives a colloidal sol, and into the final range of products which give clear solutions. Obviously, as the number of side chains in the phenolic nucleus increases, and as their length in- 11 creases, the hydrophobic character both or the phenol and subsequent derivatives, have been increased. If the pyridinium compound obtained from any particular experiment does not show significant hydrophile character, then such hydrophile character can be obtained by the very simple expedient of increasing the repetitious ether linkage, and particularly by using ethylene oxide in preference to propylene oxide. Everything else being equal, the fewer the alkyl side chains, the shorter the length of the alkyl side 12 gen of the radical Nim through its alpha carbon atom; NER4 represents a radical of a heterocyclic I compound of the pyridine series selected from the residues are substituted monocyclic phenol radichains, the lower the molecular weight of the alpha-chloromonocarboxy acid radical, and the lower the molecular weight of the pyridine type compound, the greater the hydrophile efiect. With these obvious factors in mind, there is no difiiculty in obtaining a compound having at least distinct hydrophile properties, and it may, in fact, as noted, be completely water-soluble.

Attention is directed to our co-pending applications for patent, Serial Nos. 586,262, 586,263, 586,266 and 586,267, filed April 2, 1945 and all issued November 4, 1947, as Patents Nos. 2,429,996, 2,429,997, 2,430,000 and 2,430,001, respectively, and Serial Nos 630,973, 630,974, 630,977 and 630,978, filed November 26, 1945.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A chemical compound of the formula:

RAE N.Ra.CO(OR1),.O O (Rio MO 0.111.111 E R;

l halogen halogen alkylalkyl- RaR in which R20 is an alkoxy radical selected from the class consisting of -C2H4O- and '-C3H60 radicals; n is a small whole number varying from 1 to 6; OC.R3 is the acyl radical of a low molecular weight monocarboxy acid having not more than 6 carbon atoms, in which an alpha-hydrocals having 2 of the 3 reactive 2,4,6 positions substituted by 2 alkyl side chains, of which at least one contains at least 3 carbon atoms and the longest of which does not contain more than 8 carbon atoms.

2. The compound of claim 1, wherein the halogen is chlorine.

3. The compound of claim 1, wherein the halogen is chlorine, and n is one.

4. The compound of claim 1, wherein the halogen is chlorine, n is one, and the alkoxy radical is C2H40.

5. The compound of claim 1, wherein the halogen is chlorine, n is one, the alkoxy radical is CaH4O-, and all alkyl radicals are amyl radicals.

\ MELVIN DE GROOTE.

BERNHARD KEISER.

REFERENCES CITED The followingreferences are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,917,258 Harris July 11, 1933 1,970,578 Schoeller Aug. 21, 1934 2,023,075 Harris 3, 1935 2,233,381 DeGroote et a1 Feb. 5, 1941 2,299,782 Allen et a1. Oct. 27, 1942 2,306,775 Blair Dec. 29, 1942 

1. A CHEMICAL COMPOUND OF THE FORMULA: 